The redox properties of a series of substituted vinylogous tertrathiafulvalenes (TTF) prepared by oxidative coupling of 1,4-dithiafulvenes (DTF) have been investigated in acetonitrile and dichloromethane. The different steps of the electrodimerization mechanism have been characterized: fast electron transfer, coupling between two cation-radicals and slow deprotonation. Through the substituent choice of DTF, it is possible to control the relative stabilities of the different redox species of the electrogenerated vinylogous TTF. According to the nature and position of the substituent, the structural changes induced by the steric interactions lead to a compression of potential (where the second electron is easier to remove than the first one), or on the contrary to a large increase of the separation between the first and second oxidation potentials (by comparison with similar molecules without steric hindrance). Density functional modeling calculations and detailed analysis of the electrochemical behavior have been used to rationalize the substituent effect. A good agreement with the occurrence of an EE mechanism in which the electron transfer is concerted with the conformation changes is found. The inner reorganization energies are low (0.35–0.45 eV) allowing a fast passage between the different conformations during the electron transfers.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The synthesis and the redox behavior of pi-redox cage-like molecules incorporating one or two 1,4-bis(1,4-dithiafulven-6-yl)benzene are reported. The shape of the voltammograms indicates that 6 and 9 undergo an oxidative coupling. The X-ray crystal structure of compound 6 is presented.

The crystal structures of the first stable α-diol from the α-halogenopyruv­amide series, 3-chloro-2,2-di­hydroxy-3-phenyl­propan­amide, C 9 H 10 ­ClNO 3 , and three products [3-(4-chloro­phenyl)-2-cyano-2,3-epoxy­propan­amide, C 10 H 7 ­ClN 2 O 2 , 3-bromo-2-cyano-2-hydroxy-3- p -tolyl­propan­amide, C 11 H 11 Br­N 2 O 2 , 3-bromo-2-oxo-3- p -tolyl­propan­amide, C 10 H 10 ­BrNO 2 ] obtained during the systematic synthesis of α-halogenopyruv­amides are reported. The crystal structures are dominated by hydrogen bonds involving an amide group. The stability of the geminal diol could be ascribed to hydrogen bonds which involve both hydroxyl groups.

Tetrathiafulvalenophane, vinylogous tetrathiafulvalenophanes and their redox behavior have been studied. The effect of cations on tetrathiafulvalenophane incorporating oxacrown ether has been investigated by electrochemistry.

The synthesis of 1,2-bis(2-thioxo-2,3-dihydrothiazol-3-yl)benzenes and 1,2-bis(2-selenoxo-2,3-dihydrothiazol-3-yl)benzenes, precursors of quasi-planar dithiadiazafulvalenes, is described. Functionalisation of these derivatives via lithiation is also reported.

Intermolecular coupling of 1,4-dithiafulvenes and intramolecular coupling of bis(1,4-dithiafulvenes) upon electrochemical oxidation have been studied. In addition we report that 1,4bis(1,4-dithiafulven-6-yl) benzene and a cyclic analogue undergo the same electrooligomerization process upon oxidation to afford a new kind of cyclophanes.

L'ouverture regioselective des 3-aryl-2-cyano-2-(methoxy et ethoxy-carbonyl)epoxydes 1 par l'acide chlorhydrique, conduit a des chlorocyanhydrines 3 substituees par OH, CN et CO 2 Me ou CO 2 Et sur le meme atome de carbone.

The addition of water or alcohol to 3-halopyruvamides, having a special interest in enzymology, permitted us to isolate stable α-diols and hemiketals, until then detected only by spectroscopic means. The reaction is not diastereoselective, but selective precipitation of only one diastereoisomer shifts the equilibrium between the two isomers. Isolated compounds were fully characterised and results discussed.

A one-pot reaction of α,α-dicyano epoxides with amine hydrohalides provides an attractive and general route to α-halo amides. A wide variety of amines (primary alkyl, aryl, amino esters, amino amides) and epoxides (monosubstituted alkyl, aryl; disubstituted alkylaryl) can be used, and α-halo amides are generally formed in good to moderate yields.

Gem-dicyano epoxides 1, when treated with hydrochlorides of hydroxylamines 2 in acetonitrile, at reflux, yield the α-chloro hydroxamic acids and derivatives 5 in good yields.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The chemical and electrochemical syntheses of bis(amino)tetrathiafulvalenes are presented as well as the organization of a his amphiphilic derivative in a Langmuir film.

A chemoselective reaction of amidines or guanidines with alpha- cyano epoxides leads to new 4-amino-5-carbethoxy or 4-hydroxy-5-cyano or 4-carbethoxy-5-aryl- imidazoles depending on the steric hindrance of the epoxides and on the reaction medium.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChemoselective Nucleophilic Attack of .alpha.,.alpha.-Dicyano Epoxides: A Simple Synthesis of .alpha.-Amino Amides, Epoxy Amidines and Their Cyclic AnalogsDominique Hurtaud, Michele Baudy-Floc'h, Albert Robert, and Philippe Le GrelCite this: J. Org. Chem. 1994, 59, 16, 4701–4703Publication Date (Print):August 1, 1994Publication History Published online1 May 2002Published inissue 1 August 1994https://doi.org/10.1021/jo00095a059RIGHTS & PERMISSIONSArticle Views170Altmetric-Citations9LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (344 KB) Get e-Alerts Get e-Alerts

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.